Hydroforming process and catalysts



United States Patent O signor to Esso Research and Engineering Company,a corporation of Delaware No Drawing. Application June 12., 1957 SerialNo. 665,589

15 Claims. (Cl. 196--50) This invention relates to a process for thepreparation of alumina based hydroforming catalysts or contacting agentsand a method ofreforming or hydroforming hydrocarbons using saidcatalyst or contacting agents.

The present application is a continuation-in-part of Serial No. 478,405,filed December 29, 1954, now abandoned, and Serial No. 483,444, filedJanuary 21, 1955, now abandoned. Serial No. 478,405, now abandoned,division of my co-pending application Serial No. 180,492, filed August19, 1950, now abandoned, and of my prior application Serial No. 60,864,filed November 19,1948, now US. Patent 2,636,865, of which Serial No.180,492, now abandoned, is a continuation-in-part. Serial No. 483,444,now abandoned, is a continuation-in-part of Serial No. 224,065, filedMay 1, 1951, now US. Patent 2,746,937.

Hydroforming is a well known and widely used process for upgradingnaphtha fractions in order to improve their octane number and enginecleanliness characteristics. Hydroforming is conducted at elevatedtemperatures of about 8501025 F., at pressures up to about 750 p.s.i.g.and in the presence of catalysts such as group VI metal oxides,preferably molybdenum oxide or a platinum group metal, preferablyplatinum distributed upon a support or carrier. Carriers containingalumina andusually consisting essentially of alumina in an adsorptive oractivated form are most commonly used to support hydroforming catalystcomponents. It has been found that very small difierences in' catalystcomposition or in the method for preparing the support or the catalystmakes for very great differences in the properties of the catalyst. Thisis particularly true in hydroforming processes wherein the catalyst isalternately under severe reducing conditions and oxidizing conditions.

Catalysts containing platinum distributed upon a variety of carriers orsupports have been described for various specific processes in the priorart. Commercial use in which the catalyst compositions are prepared.This field has been the subject of intensive investigation in an effortto prepare compositions having improved activ ity which are stableenough for commercial use.

Laboratory studies with platinum catalysts based on the work of Zelinskiand other Russian workers over the past 50 years have reportedm'any'compositions of high initial activity in hydrogenationanddehydrogenationtypereactions, including their use in the selective conversion of light liquid hydrocarbons. Experience has shown, however,that it is important to use purified feed stocks and mild operationconditions in these experiments. This is because these highly activecatalysts are easily poisoned by sulfur, and they. tend to-destroy theirown activity by side reactions leading to the formation of coke or tarrydeposits at even slightly elevated temperatures. Furthermore, while thevalue of the noble metal is enough to justify reworking spent catalystto recover the platinum and remake the desired composition on alaboratory scale, the cost of the metal and the ne cessity of suchreworking has been an important deterrent in the way of large-scale use.

It is the object of this invention to prepare hydroforming catalysts ofgood activity and selectivity characteristics and which moreover havegood stability or are capable ofretaining their activity and selectivitycharacteristics after prolonged use in normal hydroforming servicewherein they are alternately exposed to reducing and oxidizingconditions.

'It' is an object of this invention to prepare catalysts having highactivity and stability in the catalytic reformin'g'or hydroforming ofcommercial feed stocks or hydrocarbon fractions boiling in the motorfuelor naphtha boiling range.

It is another object of this invention to devise a novel method forpreparing platinumor palladium-containing catalyst compositions. It isalso an object of this invention to devise a new method for preparingplatinumalu'rnina or palladium-alumina composite catalysts of highactivity and stability in a simple, facile manner.

It is a further object of this invention to prepare new hydroformingcatalysts of high activity and selectivity thereof in hydrocarbonconversions such as petroleum refining has been limited, however,because of the high cost of the platinum and also because of thedifficulty of preparing the catalyst in a form which is sufiicientlyactive for the conversion and which will retain this activity withoutbeing adversely affected by contaminants in the usual hydrocarbon feedstocks. Greensfelder US. Patent No. 2,317,693 discloses the addition ofsmall amounts of platinum or palladium as a promoter to chromia-aluminacyclizing catalysts. US. Patent 2,478,916 discloses a process forreforming straight run gasolines in contact with catalysts prepared bycompositing platinum or palladium with a dry cracking component such assilica-alumina, silica-magnesia, silica-zirconia or the like. US.Patents 2,479,109, and 2,479,110- disclose the reforming of naphthafractions in contact with certain catalysts comprising platinum, aluminaand from about 0.1 to about 8 wt. percent of halogen, using a-carrierderived from a washed alumina gel. The activity and stability of theseplatinum-containing catalysts are sub- "ject to substantial variationsdepending-upon the manner comprising group VI metal oxides upon asupport.

Another object of this invention is the novel catalysts prepared by themethod described hereinafter;

It is a further object of this invention to hydroform naphtha'orgasoline fractions in contact with catalysts prepared as describedhereinafter. These and other objects will appear more clearly from thedetailed specification and claims which follow. It will be understoodthat while this description refers at places primarily to platinum andthe preparation or use of Pt-containing catalysts, the same techniquescan be employed to advantage in the preparation and use of analogouscatalysts containing palladium or certain other noble metals such asrhodium, on an alumina base. Similarly where the description'refers' tomolybdenum oxide, it will be understood that essentially the sametechniques can be employed for the preparation of other group VI metaloxide hydroforming catalysts.

It has now been found that catalysts which are especially effective forthe hydroforming of naphtha fractions may be prepared by supportingplatinum (or palladium) or group VI metal oxides on alumina preparedfrom an aluminum alkoxide. The catalytic properties of catalysts on suchbases are outstanding. It has been found that oxide.

The aluminas used as a catalyst support in accordance with the presentinvention are pure forms of active alumina prepared by hydrolysis of analuminum alkoxide such as aluminum ethylate, aluminum isopropylate,aluminum butylate, aluminum amylate, and the like. An aluminum alkoxidederived from a substantially water insoluble alcohol containing 4 ormore carbon atoms is preferred, because of the ease of recovery of theinsoluble alcohols in anhydrous form for re-use in the preparation offurther amounts of aluminum alkoxide. These alkoxides or alcoholates ofaluminum may be prepared in a variety of ways and converted tocatalytically active alumina supports, as described in detail by thepresent applicant in a prior US. Patent 2,636,865 entitled Preparationof Alumina-from Higher Alcoholates of Aluminum. Aluminas prepared .bythe hydrolysis of an aluminum alkoxide or alcoholate may be describedgenerically as alcoholate aluminas.

A number of important advantages are realized by using such analcoholate alumina as the support for reforming or hydroformingcatalysts, according to the present invention. Foremost, of these is thehigh activity of these catalysts, which can be used in naphthahydroforming, for example, to give a product of significantly higheroctane rating at a given yield than that obtained with similar catalystsupon other alumina supports. Another important advantage lies in costand ease of manufacture. Pure alumina is derived directly from thehydrolysis of an aluminum alcoholate without any washing of thehydrolysis product, because there are no inorganic cations or anionspresent to be removed. The washing of alumina gels as described in theprior art to remove foreign materials such as sodium or chloride orsulfate ions formed during the hydrolysis of the corresponding aluminateor aluminum salt is tedious and costly, because the gels are hard tofilter and these ions are strongly adsorbed. Furthermore, the washedproduct obtained in these prior art processes is never entirely pure,because the purer it becomes on washing, the harder it is to filter.

If an alumina gel is desired, the slurry of hydrous alumina obtained asdescribed above may be dried and ac tivated by application of heat. Ifit is desired to modify the properties of the gel, the slurry may betreated in various ways before drying, i.e., the hydrogen ionconcentration may be adjusted, anaging treatment at controlledtemperatures maybe used, or a peptizing agent may be added to convertthealumina into a-hydrosol.

If an alumina based catalyst is desired, the slurry of hydrous aluminamay betreated with an impregnating solution of a catalytic materialbefore drying, e.g. a solution of ammonium molybdate, chromic acid, orother catalytic or promoter agent may be added to the slurry. Ifdesired, the aqueous solution used to hydrolyze the aluminum alcoholatemay be a solution containing a catalytic or promoter agent.

The platinum '(or palladium) may be added to the alumina in any desiredmanner. For example, an impregnating solution of 'chloroplatinic acid,ammonium chloroplatinate or-palladium chloride may be prepared and mixedwith the alumina, either before or after the wet slurry is dried to formthe active alumina base. This solution may be usedby itself or inadmixture with an added halide and the composite may then be heated toconvert the catalytic'metal compound to the metal and, if necessary,activating the composition by heating to elevated temperatures orpassing a reducing gas over the composite at temperatures'of about 500to 1000 F. until the composite shows the desired activity. In the eventthat the platinum or palladium compound is not readily decomposed byheating, then the composite may first be treated with hydrogen sulfideto fix the catalytic metal followed by drying and'heating, in'thepresence of a reducing gas'if necessary. Alternatively, theplatinumor palladium saltsolution may be treated with hydrogen sulfide and theresultant brown solution or sol then maybe mixed with the alumina. Themetal-containing solution is ordinarily added in the form of acommercially available halide such as chloroplatinic acid, whichcontributes halogen to the composition. The platinum or palladiumcompound should be added to the alumina in sufficient amount that thefinal catalyst contains from 0.01 to 2 or even 4 or more wt. percent ofplatinum or palladium, preferably, from 0.1 to 2 wt. percent of platinumor from 0.5 to 3 Wt. percent of palladium.

In some cases it may be desirable to incorporate from about 0.1 to 4 wt.percent of added halogen in the catalyst composition, beyond thatordinarily introduced with the chloroplatinic acid or similar metalhalide impregnating solution. This may be accomplished by addinghydrogen fluoride, hydrochloric acid or a halogen compound such asammonium fiuoride, ammonium acid fluoride, aluminum chloride or the liketo the platinum (or palladium). solution before compositing the samewith the alumina, or it may be added to the platinumorpalladiuin-containing composite.

Still another advantage of using aluminum alcoholate as the source ofthe alumina base according to the present invention lies in itsversatility and ease of handling. The alcoholate may be hydrolyzed andthe initial product converted to various forms of dry alumina by any oneof a number of ways, all of which benefit from the fact that no washingis required to give a pure alumina as the final product. Thus, the priorUS. Patent 2,636,865 mentioned above describes the hydrolysis usingeither water or an aqueous solution, such as dilute acetic acid or ahydrosol, and the hydrolyzed product may be aged, peptized,'or adjustedas to temperature or hydrogen ion concentration in any Way desired tomodify the properties of thefinal dried gel. Many changes are likewisepossible in the final drying or activation-steps. A number of differentalcoholate aluminas have been found to form excel lentplatinum-on-alumina and molybdenum oxide on alumina catalysts fornaphtha reforming, and all of these modifications retain the advantagesnoted in alumina purity and ease of manufacture.

Among other modifications .of the basic procedure, the alcoholate may behydrolyzed by a solution containing the catalytic agent, instead ofimpregnating the wet alumina slurry or a peptized sol or dried aluminabase derived therefrom. Thus, one particular method of treating thealuminum alcoholate which may be used to advantage in the preparation ofthese catalysts may be to convert it into an alumina hydrosol in themanner described in Hunter and Kimberlin U.S.. Patent No. 2,656,321, andthen combine this hydrosol with a suitable platinumorpalladium-containing solution in the manner described. This conversiontothe hydrosol may 'be accomplished by adding a small amount of apeptizing agent such as glacial acetic acid to the aluminum alcoholatedissolved in an excess of alcohol or in a hydrocarbon solvent, followedby hydrolyzing the alcoholate containing the peptizing agent byvigorously mixing the water, preferably at about 15 0- 200'F., andrecovering the alumina hydrosol thus produced. The preferred hydrosolscontain about 1 to 6 wt. percent alumina, in an extremely high degree ofdispersion, and show no tendency to settle upon standing in a quiescentstate. Upon drying, this type of sol produces a clear, glassy aluminagel in contrast to the chalky gel produced by the usual peptizedprecipitates of alumina. It is also possible to set theplatinum-containing sol to a hydrogel and then proceed with the furtherpreparation. Where additional halogen is desired in the catalyst, thismaybe added to the platinum-containing solution either before'or afterthe sol is composited therewith, or it may he-added'to the hydrogel ifone is formed.

Alternatively, the sol or gel' containing the platinum salt may be driedand the dry gel treated with a suitable gaseous or aqueous halogencompound or solution. Afteradding the platinum (or palladium) compoundto the-alcoholate alumina and aftersulfiding or halogen addi- E3 tioiiasdesired, the finished catalyst is produced by drying at a moderatetemperature of about 200 to 400 F. and calcining. Before use forreforming, the catalyst may be reduced if desired by treatment withhydrogen or a recycle gas from the hydroforming process. This reductionmay be carried out, for example, by treating the pilled catalyst with asuitable hydrogen-containing gas at 500 to 1000 F. for 1 to 3 hours.

Group VI metal oxides may be composited with the alcoholate alumina invarious ways. As a typical example, molybdenum oxide can be compositedwith the hydrous alumina slurry or with the dried and adsorptive aluminaby mixing a solution of ammonium molybdate therewith. Alternatively, amolybdic oxide sol or dry molybdic oxide or a water slurry of molybdicoxide may be mixed with the alumina and fixed thereon by heating toelevated temperatures of about 1000-l200 F. The amount of group VI metalcompound added is somewhat variable. -In the case of molybdenum, theamount added is usually sufficient to provide from about 1 to about 15wt. percent molybdic oxide in the catalyst composition while forchromium the amount added should be sufiicient to provide about 5 to 40wt. percent chromic oxide in the catalyst composition.

According to this invention, petroleum naphtha and similar hydrocarbonmixtures containing appreciable quantities of naphthenes can besubjected to a reforming operation to yield a liquid product of improvedoctane number boiling within the gasoline range. Depending upon reactionconditions, catalytic reforming operations are generally referred to aseither hydroforming or aromatization reactions. By hydroforming isordinarily meant an operation conducted at elevated temperatures andpressures in the presence of a solid catalyst and added hydrogen whereina hydrocarbon fraction is increased in aromaticity and wherein there isno net consumption of hydrogen. The term aromatization refers to anoperation in which a hydrocarbon or hydrocarbon fraction is treated atelevated temperatures but at substantially atmospheric pressure in thepresence of a solid catalyst for the purpose of increasing thearomaticity of the hydrocarbon or hydrocarbon fraction.

Catalytic reforming operations are usually carried out at temperaturesof around 850 to 1100 F. in the presence of such catalysts as platinumor other platinum group metal, molybdenum oxide, chromium oxide and thelike. In accordance with this invention these catalysts are usuallysupported on a base or carrier consisting essentially of alumina derivedfrom aluminum alcoholate. Reforming is effected at elevated pressures,preferably about 50 to about 500 p.s.i.g., and in the presence ofhydrogen or hydrogen-rich process gas in amounts of from about 500 to7,500 s.c.f. per barrel of liquid naphtha feed. The catalyst may be inthe form of a fixed or moving bed through which the vaporizedhydrocarbon feed and hydrogen is passed or the so-called fluidizedsolids technique may be used in which the catalyst in finely dividedform is suspended in the reactant vapors. In the moving bed andfluidized solids technique, the catalyst is continuously circulated fromthe reforming zone to a regeneration zone wherein the inactivatingcarbonaceous materials deposited on the catalyst during reforming areburned off with air or oxygen-containing regeneration gas. In fixed bedoperation it is necessary periodically to take the reactor elf-streamand regenerate it.

The invention is further described and illustrated by the followingexamples.

EXAMPLE 1 270 grams of aluminum were dissolved in liters of a mixture ofanhydrous normal amyl alcohol and a petroleum distillate boiling withina range of from 300 to 400 F. The mixture of alcohol and petroleumdistillate was in a ratio of one part of alcohol to one part ofpetroleum distillate, by volume. A small amount of mercuric chloride,about 0.001 part of mercuric chloride perpart of aluminum metal byweight was added. To initiate thev The aqueous slurry of hydrous aluminawas concentrated by settling to approximately 8% solids content. Therewere then added to the alumina slurry 680 cc. of ammonium molybdatesolution containing 55.5 grams of molybdenum oxide. The mixture wasdried in an oven at 240 F. and then activated by heating at 850 F. j

The product was a hard, adsorptive catalyst comprising 10% molybdenumoxide on alumina gel. Its surface area was 380 square meters per gram.This cata lyst was used to hydroform an East Texas virgin naphthaboiling within a range of 267 to 418 F. and having a CPR-research octanenumber of 41.7. In the series of runs, the following operatingconditions were established:

Pressure, p.s.i.g. 200 Average catalyst temp., F. 929 V./v./hr. .97Hydrogen, c.f./b. 1970 Volumes of liquid feed per volume of catalyst perhour.

Cubic feet of hydrogen under standard conditions per barrel of feed.

Under these conditions, the following yields were obtained:

Gasoline, vol. percent 82.0.

CPR-Research octane no. 95.0

Carbon, wt. percent on feed .20 EXAMPLE 2 432 g. of aluminum turningswere dissolved in 16 liters of a 50-50 mixture of anhydrous normal amylalcohol and a petroleum distillate boiling in the range of from 300 F.to 400 F. A small amount of mercuric chloride, about 0.0005 part ofmercuric chloride, per part of aluminum by weight, was used as acatalyst to dissolve the metal. To initiate the reaction, the mixturewas heated to boiling by means of a steam coil. After the reaction waswell started, cooling was necessary. The cooling was done by means of acoil immersed in the reaction mixture. Toward the end. of the reaction,the mixture was again heated to complete the solution of the metal.About 30 minutes is required for the reaction between the aluminum andthe alcohol by the procedure described. 7

The solution of aluminum amylate thus obtained was hydrolyzed with 16liters of distilled water. The hydrolysis was accomplished by pumpingthe aluminum amylate solution and the water simultaneously through asmall centrifugal pump. The feed lines to the pump were so constructedthat the two streams were mixed just before reaching the impeller of thepump. The discharge from the pump was placed in a vessel and allowed toremain quiescent for about 10 minutes at the end of which time thepetroleum distillate-regenerated alcohol mixture and the aqueous slurryof alumina had separated as two distinct liquid layers. The petroleumdistillate-regenerated alcohol layer was decanted and dried bydistilling off the small amount of water and reused in a subsequentpreparation without further treatme-nt.

To the layer comprising the aqueous slurry of alumina was added aceticacid in the ratio of about 5 liters of acetic acid per pounds ofaluminum metal. After standing for 1 hour, there were then added to theacidi-. fied alumina slurry 1000 cc. of an ammonium molybdate solutioncontaining approximately 90.5 g. of molybdenum 7 oxide. The mixture wasdried in an -oven at 250 F. and then activated by heating to 850 F.

The product was a hard, adsorptive material comprising 10% molybdenumoxide on alumina gel. its surface area was 372 square meters per gram.An East Texas virgin naphtha boiling 'in the range of 267 F. to 418 F.and having a CPR-research octane number of 41.7 was passed over thiscatalyst under conditions of 930 -F., 200 p.s.i.g., a feed rate of 0.49volume of naphtha per volume of catalyst per hour and with hydrogenintroduced into the reactor at the rate of 1580 standard cubic feet perbarrel of naphtha feed. The process period was 12 hours. There wasobtained a liquid product and 75.5 volume percent yield based on thenaphtha feed having a CPR-Research octane number of 100.1.

After the process period was completed, the catalyst was regenerated byburning ofi carbon amounting to 0.79 weight percent of naphtha feed.After regeneration, the process period feeding naphtha was repeated.

EXAMPLE 3 A slurry of hydrous alumina was prepared from 432 g. ofaluminum metal as described in Example 2. Acetic acid in the ratio of '5liters of acetic acid per 100 lbs. of aluminum metal was added to theslurry. Then after standing for 24 hours, there were added to theacidified alumina slurry 1000 cc. of a solution containing approximately90.5 g. of molybdenum oxide. The mixture was dried in an oven at 250' F.and then activated by heating at 850 F.

The product was a hard, adsorptive material .COIIP. prising molybdenumoxide on alumina gel. Its surface area was 405 square meters per gram.It is useful in hydroforming processes.

EXAMPLE 4 A slurry of hydrous alumina was prepared from 432 g. ofalumina metal as described in Example 2. .110 cc. of ammonium hydroxidesolution containing 27 g. of ammonia were added to the alumina slurry.There were then added 1000 cc. of an ammonium molybdate solutioncontaining approximately 90.5 g. of molybdenum oxide. The impregnatedslurry was dried in an oven at 250 F. and then activated by heating to850 'F.

The product was a hard, adsorptive material comprising 10% molybdenumoxide on alumina gel. :Its surface area was 328 square meters per gram.It is useful in hydroforming processes.

EXAMPLE 5 A slurry of hydrous alumina was prepared from 432 g. ofaluminum metal as described in Example 2. The slurry was dried in anoven at 250 F. The dried alumina gel was ground to a powder and thenthoroughly mixed with 500 cc. of a solution of ammonium molybdatecontaining approximately 90.5 g. of molybdenum oxide. The gel was thenredried in an oven at 250 F. and activated by heating to 850 F.

The resultant impregnated, activated gel comprised 10% molybdenum oxideon alumina gel and had a surface area of 388 square meters per gram. Itis very useful in hydroforming processes.

EXAMPLE 6 A slurry of hydrous alumina was prepared from 432 g. ofaluminum metal as described in Example 2. To this slurry was added insuccession 500 cc. of .a solution of calcium nitrate containingapproximately 23.4 g. of calcium oxide and 1000 cc. of a solution ofammonium molybdate containing approximately 93.4 g. of molybdenum oxide.The impregnated slurry was then dried in an oven at 250 F. and the drygel was activated by heating .to 850 F.

The product was a hard, adsorptive catalytic material comprising 87.5%aluminum oxide, 10% molybdenum 8 oxide and 2.5% calcium oxide. It had asurface area of 343 square meters per gram. This catalyst was used tohydroform an East Texas virgin naphtha boiling within .a range of 267 to418 'F. and having a CPR-Research octane number of 41.7. :In the seriesof runs, the follow ing operating-conditionswere established:

Pressure, p.s.i.g .200 Average catalyst -temp., F. 930 V./v./hr. 0.94Hydrogen, c.f./b. 1530 Volumes of liquid feed per volume of catalyst perhour. 2 Cubic feet of hydrogen under standard conditions per barrel offeed.

Under these conditions, the following yields were -obtained:

A solution of aluminum amylate was prepared as described in Example 2 bydissolving 432 g. of aluminum metal in 16 liters of a 50-50 mixture ofamyl alcohol and a petroleum distillate boiling in the range of 300 F.to 400 F. in the presence of 0.2 g. of mercuric chloride.

A silica hydrosol was prepared by passing 3650 cc. of a solution ofsodium silicate (Na O.3.25SiO containing 30 g. of silicon dioxide perliter through a bed of 2250 cc. of an acid regenerated cation exchangeresin. Any commercial cation exchangeresin such as an insoluble polymerprepared from acidic monomers such as phenols, phenol sulphonic acid orphenol carboxylic acid, on a sulphonated carbonaceous material such assulphonated coal, sulphonated peat, etc. may be used. Amberlite IR-l00(Resinous Products Co.) believed to be made by reacting a phenolsulphonic acid with formaldehyde was used in this example. This solprepared in this manner gave an acid reaction toward litmus andcontained approximately 28 g. of silicon dioxide per liter.

1570 cc. of the above silica sol was diluted to 16 liters with distilledwater and this diluted sol was used to hydrolyze the aluminum amylatesolution. The hydrolysis Was accomplished by passing the two liquidssimultaneously through a centrifugal pump as described in Example 2.Upon settling there formed an aqueous slurry of hydrous alumina andhydrous silica from which the petroleum distillate-regenerated alcoholreadily separated as a separate liquid layer. This liquid layer wasdecanted and dried by distilling oil the residual water and was reusedin a subsequent preparation without further treatment.

The aqueous slurry of hydrous alumina and hydrous silica thus preparedwas mixed with 1000 cc. of a solution of ammonium molybdate containingapproximately 95.5 g. of molybdenum trioxide. The mixture was dried inan oven at 250 F. and activated by heating to 850 F.

The resultant impregnated alumina-silica gel was com prised of 85.5%aluminum oxide, 4.5% silicon dioxide and 10% molybdenum oxide and had asurface area of 452 square meters per gram. It is useful as ahydroforrning catalyst.

EXAMPLE 8 An aqueous slurry of hydrous alumina and hydrous silica wasprepared according to Exmple 7. Acetic acid was added in the ratio of 5liters of acetic acid per pounds of aluminum metal and the mixture wasallowed to set for 24 hours. There were then added 1000 cc. of ammoniummolybdate solution containing approximately 95.5 g. of molybdenum oxide.It was then dried in an over at 250 F. and activated by heating at 850F.

The product whichis useful as a hydroforrning catalyst was a hardadsorptive material comprising 85.5% aluminum oxide, 4.5% silicondioxide, and 10% molybdenum A slurry of hydrous alumina was preparedfrom .432 g. ofaluminum metal as described in Example 2. The slurry wasevaporated in an oven to a solids content of 12.5%. To this was added650 g. of dry process zinc oxide made by burning Zinc metal in air andacetic acid in the ratio of liters of acetic acid per 100 pounds ofaluminum metal. The mixture was mixed in a ball mill for 1 hour. Thenthere were added 184 g. of powdered ammonium molybdate (81.4% M00 andthe ball milling was continued for an additional 1.5 hours. The mixturewas then dried in an oven at 250 F. and activated by heating to 850 F.

The product was a hard, adsorptive material comprising 90% zincaluminate and molybdenum oxide and had a surface area of 209 sq. metersper gram. It is useful as a hydroformiug catalyst.

EXAMPLE 10 A slurry of hydrous alumina was prepared from 432 g. ofaluminum metal as described in Example 2. The slurry was thenimpregnated with 200 cc. of a solution of cerium nitrate containingapproximately 7.5 g. of cerium oxide (Ce O 300 cc. of a solution ofpotassium dichromate containing approximately 10.9 g. of potassium oxideand approximately 17.6 g. of chromium oxide (Cr O and 500 cc. of asolution of ammonium dichrom-ate containing approximately 108.6 g. ofchromium oxide. The mixture was dried in an oven at 250 F. and activatedby heating at 850 F.

The product was a hard, adsorptive material comprising 86.6% aluminumoxide, 11.5% chromium oxide, 1.1% potassium oxide, and 0.8% ceriumoxide, and had a surface area of 343 square meters per gram. It isuseful as an aromatization or low pressure (25-75 p.s.i. .g.)hydrofonning catalyst.

EXAMPLE 11 A slurry of hydrous alumina was prepared from 432 g. ofaluminum metal as described in Example 2.

A silica hydrosol containing approximately 28 g. of silicon dioxide perliter was prepared as described in- Example 7.

2040 cc. of the silica hydrosol were added to the hydrous aluminaslurry. It was then impregnated with 100 cc. of a solution of ceriumnitrate containing approximately 18.2 g. of cerium oxide, 200 cc. ofpotassium dichromate containing approximately 13.6 g. of potassium oxideand 22 g. of chromium oxide, and 800 cc. of a solution of ammoniumdichromate containing approximately 140 g. of chromium oxide. Themixture was dried in an oven at 250 F. and then activated by heating to850 F.

The product was a hard, adsorp tive material comprising 76.5% aluminumoxide, 5.4% silicon dioxide, 15.2% chromium oxide, 1.8% cerium oxide,and 1.7% potassium oxide. It had a surface area of 382 square meters pergram. It is useful in aromatizatio-n or low pressure (2575 p.s.i.g.)hydroforming processes.

EXAMPLE 12 The catalyst resulting comprised 90% aluminum oxide.

and 10%vanadium oxide. l t hadla surface area of ".10 square meters pergram. This catalyst is useful forfhy' droformin-g or dehydrogenationprocesses.

w EXAMPLE 13 A slurry of hydrous alumina was prepared from 432 g.

of aluminum metal as described in Example 2. This was impregnated with98 g. of soluble tungstic acid dissolved in approximately 2 liters ofwater containing cc. of 28% ammonia. 75 cc. of acetic acid were added tothe impregnated slurry and the mixture was dried in an oven at 250 F.and activated by heating to 850 F.

The resultant catalyst comprised aluminum oxide and 10% tungstentrioxide and had a surface area of 291 square meters per gram. It isuseful for hydrogenation and catalytic cracking processes.

EXAMPLE 14 r 27 g. of aluminum were dissolved in 1 liter of 50/50 normalamyl alcohol-petroleum distillate solution as de-[ canted and dried forreuse as described in Example 1.

The slurry was placed in an oven at 220 F. After a few hours in theoven, the alumina had become peptized forming a hydrosol rather than theslurry of gelatinous alumina.

The alumina hydrosol was concentrated to approximately 6% solid contentby evaporation and was emulsified with approximately 10 times its volumeof naphtha, using Aerosol as an emulsifying agent. A small amount ofmorpholine was addedto the oil prior to the emulsification so as to givethe sol a pH of about 9 after emulsification which is favorable for thegelation of the alumina sol. The gelation occurred rather rapidly butthe mass was stirred during the entire setting period which is completedin about an hour. The gel particles were separated by filtration andactivated by heating to 850 F. The sizes of the gel microspheres soformed were of 60 to microns and were of uniform shape. This material isan excellent base or support for molybdenum oxide or platinum and may bereadily converted to active hydroforming catalyst by impregnation withammonium molybdate solution in sufficient amount to pro vide 10 wt.percent M00 in the composite or with chloroplatinic acid in suflicientamount to provide 0.1 to

0.6 wt. percent platinum in the catalyst.

EXAMPLE 15 Aluminum alcoholate solution is made batchwise by the,following procedure. 432 grams of aluminum turnings are dissolved in 16liters of a mixture of anhydrous amyl alcohol and a petroleum distillateboiling within ing.

The solution of aluminum amylate thus prepared is hydrolyzed by mixingwith 16 liters of distilled water at about 80 F. The hydrolysis reactionis practically instantaneous and is accomplished by simultaneouslypumping the aluminum amylate solution and the distilled water through asmall centrifugal pump. This forms an aqueous slurry of hydrous alumina,from which the petroleum distillate-regenerated alcohol mixtureseparates readily as a supernatant layer. This liquid layer, is decantedand dried by distilling off thewater audr e used in a subsequentpreparation without further treatment. 7

The alumina slurry is allowed to settle overnight and a layer of clearwater is then decanted, leaving a concentrated slurry containingapproximately 8% alumina. This concentrated slurry is dried in an ovenat about 220250 F. This base is activated by calcining for 9 hours aftergradually raising the temperature to 900 F. The product is a pure,highly adsorptive alumina gel. 498 grams of this base are thenimpregnated with a solution containing 67 grams of 10% aqueouschloroplatinic acid diluted to 425 cc. in distilled water. Theimpregnated catalyst is dried at room temperature, and further driedovernight at 250 F., to give an active hydroforming catalyst comprising0.5 wt. percent Pt on an alcoholate alumina base. For use in a fixed bedhydroforming operation the dried catalyst is formed by compression intocylindrical pills having a diameter of 95 and a length of A EXAMPLE 16The hydroforming activity of the alcoholate alumina base catalystprepared according to Example 15 is shown by test data obtained usingthe pilled catalyst in a fixed bed catalyst test unit under thefollowing operating conditions:

Pressure, p.s.i.g 200 Average catalyst temperature, F 900 Hydrogen, cu.ft. per bbl. of feed 6000 Oil feed, lbs./hr./lb. of catalyst 1 Reactionperiod, hours 4 Under these conditions of 200-330 F. heavy virginnaphtha having an initial Research clear octane number of 51.3 isconverted to a total liquid product of 103.4 Research clear octanerating. Following regeneration by burning in diluted air, the samecatalyst in a second cycle gives a product of 100.6 octane in 74.3volume percent yield, plus 12.5% of total C or a C 430 F. yield of 86.8volume percent on feed.

EXAMPLE 17 An active p'latinum-alumina-fluoride catalyst is prepared onan alcoholate alumina base as follows: 855 grams of the dried (250 F.)alumina base prepared as in Example above is pulverized and formed intoa paste with 500 cc. of a dilute aqueous solution containing 16 grams ofhydrogen fluoride, contacted overnight at room temperature and thendried for 16 hours at 250 F. The powdered catalyst support prepared inthis manner is worked into a paste with 500 cc. of an aqueous solutioncontaining 7.5 grams of chloroplatinic acid, and then platinum sulfideis precipitated by bubbling hydrogen sulfide through the paste for 1%hours. After drying at 250 F. the catalyst is pilled and calcined for 2hours at 950 F. The active catalyst thus prepared is found on analysisto contain 0.41 wt. percent of Pt and 1.63 wt. percent of fluoride.

EXAMPLE 18 864 g. aluminum metal turnings are dissolved in 32 liters ofa 50-50 mixture of Pentasol (mixed amyl alcohols) and a 240 to 280 F.petroleum naphtha cut, adding about 0.86 g. of HgCl as a catalyst topromote the reaction. When the reaction is complete the resultingaluminum amylate solution is mixed in rapid se quence with 1) 544 gramsof glacial acetic acid dissolved in about 20 liters of a 50-50 mixtureof Pentasol and petroleum naphtha and with (2) 117 lbs. of distilledwater heated to about 180 F. The mixing is accomplished by means of twosmall centrifugal pumps. In the first pump the aluminum amylate solutionis mixed with the acetic acid solution in volumetric ratio of about 3 to2 and in the second pump the discharge from the first pump is mixed withthe distilled water in volumetric ratio of about 1 to 1.

The mixture is then discharged into a vessel and allowed to stand for 10minutes, during which time it separates into two layers. The uppernon-aqueous layer comprises the major portion of the alcohol andhydrocarbon used, which is here drawn OE and dried for re-use inreaction with additional aluminum metal. The lower aqueous phasecomprises an alumina hydrosol containing about 3% by wt. of A1 0 andabout 1% by wt. of acetic acid.

This hydrosol is then charged to a stripping vessel and heated to takeover-head any residual alcohol or hydrocarbon in the sol. Water takenover-head may be returned to the hydrosol. The product hydrosol is clearand dries to form a transparent glassy gel.

12 liters of this 3% alumina hydrosol (about 360 g. A1 0 is agitated ina crock with a lightning mixer, and to it is added 19.1 g. of 10%aqueous H PtCl .6H O (0.72 g. Pt). Agitation is continued 30 minutes andthe hydrosol is then dried at 240 F. to form an active gel catalysthaving a nominal composition of 99.8Al O 0.2Pt

EXAMPLE 19 Ten liters of an alumina hydrosol prepared according toExample 18, containing about 310 grams A1 0 are charged to a crock.There is then added thereto with mild agitation at room temperature amixture containing 6.57 grams of 48% aqueous HF and 43.2 grams of 10%aqueous H PtCl .6H O (3.15 grams HF and 1.63 grams Pt). Localizedgelation takes place during this addition, and the mixture ishomogenized by agitation overnight. The homogenized mixture is treatedby bubbling a vigorous stream of hydrogen sulfide through it for 30minutes and sutficient 28% aqueous NH OH is added to adjust the sulfidedmixture to a pH of between 5.0 and 6.0. The mixture is then dried at 250F. giving a catalyst comprising 98.5Al O -0.5Ptl.0HF.

The catalyst thus prepared is ground and pilled, and charged to a fixedbed testing unit. It is activated by heating for 12 hours at 900 F.under a hydrogen pressure of 200 p.s.i.g., and then used to hydroform a200- 330 F. virgin naphtha cut having an initial research clear octanenumber of 49.4, under the same conditions of temperature and feed ratedescribed above in Example 16. In an extended test where the reactionmixture is passed over the catalyst for five 3 hour cycles alternatingwith hydrogen flow in the absence of feed for 6 hours, to regenerate thecatalyst by removing incipient deposits therefrom, the composite liquidproduct for 5 cycles has a clear research octane number of 100.9. Thisproduct is recovered in a 87.3 volume percent yield of C 430 F. product.

EXAMPLE 20 Ten liters of aluminum amylate solution prepared as inExample I are hydrolyzed at a temperature below 60 F. by stirring into30 liters of cold water, over a period of 30 minutes, and after stirringfor an additional 15 minutes and settling for about an hour the organiclayer is decanted from the alumina slurry. To twice this quantity ofslurry thus prepared, 162 cc. of 10% aqueouschloroplatinic acid is addedand stirred for a total of about 25 minutes, and the impregnated slurryis dried at 250 F.

The active catalyst prepared in this way is pilled and tested as inExample 16. Under these conditions a 220- 330 F. naphtha feed having aninitial Research octane rating of 58.4 is converted to an 83 volumepercent yield of a 95.0 octane number product, at a weight spacevelocity of 1.6 pounds of oil per hour per pound of catalyst.

EXAMPLE 21 Palladium catalysts of high activity can also be preholatesolution at room temperature is dried and calcined for 4 hours at 1100F.; 786 g. of this dried base is impregnated With 786 cc. of an aqueoussolution containing 26.1 g. of PdCl (60% Pd) and 35 cc. of concentratedHCl. The resulting composite is dried at room temperature and at 250 F.,pilled, and brought up to reaction conditions in the testing unit fortesting according to the standard test procedure. The naphtha product isfound to have a Research clear octane rating of 99.0, obtained in a C430 F. yield of 88.0 volume percent on feed at a Weight space velocityof 2. The excellent stability of this catalyst is shown by a heat agingtest in which a sample heated for 64 hours at 1250 F. is stillsufiiciently active to give a 90.5% yield of 94.5 O.N. product in thesame standard test, even though such heating is severe enough todeactivate ordinary noble metal catalysts.

EXAMPLE 22 The known harmful eifects of sodium or sulfate as impuritiesin an alumina base for hydroforming catalysts are found also to besuificiently severe to prevent the formation of a highly active catalystwhen these ions are added during the preparation of a platinum catalyston alcoholate alumina. Thus, in one experiment where the alcoholatealumina base prepared as in Example 15 is treated with a dilute solutionof sodium methyl siliconate to give a base containing 0.5% sodium as NaO and 1.0% SiO and then impregnated with the platinum solution to give acatalyst containing 0.6 wt. percent Pt, the final catalyst tested as inExample 16 gives an octane increase from only 58.4 (feed) to 70.9(product), at a feed rate of 1 pound of oil per hour per pound ofcatalyst.

Another catalyst is prepared by hydrolyzing the alumimun alcoholate withwater saturated with S and then removing excess S0 by treating theslurry of hydrous alumina with an ion exchange resin (Amberlite IRA-400,hydroxyl form). This slurry is filtered to remove the resin and driedand calcined to give an alumina base which still shows a qualitativetest for sulfate ions. A sample of this base is impregnated with a PtShydrosol made by adding ammonium polysulfide solution (20%) to achloroplatinic acid solution equivalent to 0.5% Pt on finished catalyst.The impregnated composite is dried and pilled for the standard activitytest. This catalyst increases the octane rating of the same feed stockfrom 58.4 to only about 77.5 at a Weight space velocity of 2 pounds ofoil per hour per pound of catalyst, which is a poor activity at best incomparison with the highly active catalysts of the present invention.

This efiect of impurities is particularly important with respect to thecost of manufacture of alumina-base catalysts, as already discussedabove. Aluminum metal which is the raw material for the alcoholatealumina base used in the present invention is much less expensive thanthe cheapest aluminum salts available commercially. But the most readilyavailable sources of aluminum compounds of even commercial purity aresodium aluminate and aluminum sulfate, and both of these materialscontain inorganic'ions which are very difiicult to remove once they areintroduced, and very harmful in a platinumalumina catalyst.

EXAMPLE 23 The excellent activity and stability of the catalysts of thepresent invention is shown by a series of activity maintenance testsconducted over an extended period of time under the same conditions oftemperature and pressure as in Example 16. The Pt-alcoholate aluminacatalyst used in these tests is supported on a base prepared essentiallyas in Example 15, hydrolyzing the alcoholate solution in this case at160 F. using 2 volumes of water per volume of alcoholate. 1100 g. ofthis alumina, dried at 250 F. and calcined at 1100' F. is impregnatedwith 16.5 of chloroplatinic acid dissolved in 1100 cc. of water, driedat room temperature and at 14 250 F., pilled and reduced in the testunit for activa tion.

This catalyst retains its high activity for over 1200,

hours of continuous operation without regeneration, at 900 F. and aweight space velocity of 2 w./hr./w. (pounds of oil per hour per poundof catalyst). During this period the product from a 51.7 octane 200430F. heavy naphtha feed ranges in octane rating from 98 to 95, with anaverage correlated yield of 84.7 volume percent C -430 product at theoctane level for this period.

This is a far more stable catalyst than those prepared by impregnatingplatinum on commercially available aluminas, even where catalysts ofhigh initial activity have been prepared on such bases. Thus, forexample, U.S. Patent 2,667,461, granted January 26, 1954, on a Method ofMaking Platinum-Containing Catalysts shows a very real advantage forplatinum on certain HF- treated commercial aluminas over similarcatalysts sup ported on a washed alumina gel prepared from aluminumchloride. The octane rating of the product obtained from the washedgel-base catalyst in that case was only 80.0, with a corresponding yieldof 98.8 volume percent on feed indicating relatively little activity ascompared to the catalysts of the present invention. This gel-basecatalyst was derived from aluminum chloride, which is also considerablymore expensive than aluminum metal. The more active catalysts thereindescribed were supported on commercial aluminas known as Alorco GradeF-10, a commercially pure product believed to be derived from athoroughly washed Bayer process alumina, and H-41, a silica-stabilizedalumina believed to be derived from sodium aluminate by precipitationwith CO in the presence of a small amount of sodium silicate. Life testsunder the conditions described above on an F-10 based catalystcontaining 0.5% Pt and 1.0% HP but omitting the sulfiding step of thispatent show a drop in activity from 100 O.N. for the fresh catalyst to92 in only sixty hours of operation at 2 w./hr./ W. A similar life teston a 0.5 Pt catalyst on H-41 alumina, prepared by direct impregnationwith chloroplatinic acid, show an activity drop of about 7 octane unitsper 100 hours at the 90 octane level, at the same weight space velocityand at the slightly higher pressure of 275 p.s.i.g., which should beexpected to give a lower deactivation rate than the 200 pounds pressureused in the above examples.

I The above examples have emphasized the advantageous results obtainedwhen hydroforming naphtha fractions in contact with catalysts consistingessentially of platinum on substantially pure alumina derived from analuminum alcoholate. Similar advantages in terms of the purity and costof manufacture of an active catalyst may also be important Where it isdesired to add small amounts of other promoter or stabilizer materialsto the composite. For example, a purified silica hydrosol,

chromic acid or zirconyl acetate may be added to the alcoholate aluminaso as to introduce silica, chromia or zirconia, respectively, into thefinished catalyst with-.

A solution of aluminum amylate is prepared as described in Example 15above. A purified silica hydrosol containing 3% Si0 is prepared bycontacting sodium silicate with an acid-regenerated cation exchangeresin (Amberlite IR- manufactured by Rohm & Haas, be-

lieved to be made by reacting a phenol sulfonic acid with formaldehyde).2700 cc. of the silica sol thus prepared is diluted to 16 liters withdistilled water, and this diluted, sol isused to hydrolyze an equalvolume of the aluminum amylate solution. The hydrolysis is accomplishedby passing the two liquids simultaneously through a centrifugal pump, asdescribed above in Example 15. Upon settling, there is formed an aqueousslurry of hydrous alumina and hydrous silica, from which the petroleumdistilled-regenerated alcohol separates as a supernatant liquid, whichis separated and dried for re-use as described. The resulting aqueousslurry of hydrous alumina and hydrous silica is dried in an oven at 250F., to give an alumina-silica catalyst base comprising 90% alcoholatealumina and silicon dioxide.

This base is activated by calcining for nine hours at 900 F., aftergradually heating to this temperature; 573 grams of this calcinedmaterial are then impregnated with 490 cc. of an aqueous solutioncontaining 7.6 grams of chloroplatinic acid. The impregnated material isdried at room temperature and then at 250 F. After pilling it is testedfor hydroforming activity according to the standard procedure outlinedin Example 16 above, without further preliminary calcining or reduction.

At a feed rate of 2 w./hr./w. (pounds of oil per hour per pound ofcatalyst), this catalyst gives a 92.5 volume percent yield of C 430product having a clear Research octane number of 96.0. Followingregeneration by burning in diluted air, a second cycle with the samecatalyst gives a total liquid product having 100.4 Research octane, atthe standard feed rate of 1 w./hr./w.

The following examples and/or tests clearly establish that asubstantially improved hydroforming process is obtained by the use ofalcoholate alumina base catalysts. In these examples or comparisons thealcoholate alumina base catalysts are identified by capital letters andthe catalysts used for comparative purposes are identified by arabicnumerals. Each of the catalysts used in Examples 25-27 is described inthe appendix following Example 27. As there indicated, all of thedetails of the preparation of certain of the commercial catalysts arenot known.

EXAMPLE 25 Table I below, shows hydroforming results comparingmolybdenum oxide hydroforming catalysts based on alcoholate alumina withcatalysts based on other commercial aluminas. The hydroforming operationwas conducted in each case with a fixed bed of catalyst maintained at900 F. at 200 pounds per square inch pressure feeding a virgin naphthafrom West Texas crude boiling in the range of 200 to 330 F. and having aResearch octane number of 48.0 and feeding dry hydrogen gas at a rate of1500 cubic feet per barrel of naphtha feed for cycle lengths of fourhours. The catalyst was regenerated between cycles by burning off cokedeposits with air. The feed rate was adjusted to give a C product havinga Research octane number of 95:

Table 1 Yield of 05+ Feed Rate,

Vol. Percent 1 Weight of naphtha feed per hour per weight of catalyst.

The superior activity of catalysts A and B is obvious from thesubstantially higher feed rates permitted thereby. All of the catalystsare equivalent in selectivity as judged by the yield of 95 octane numberproduct.

EXAMPLE 26 16 before, the feed rate was adjusted to give a 95 octanenumber product:

Table II 5 Feed Rate, C5+ Product Catalyst W./Hr./W. D+I;p@ 212 EXAMPLE27 In order to test their stability under hydroforming conditionssamples of several catalysts were placed in screen containers which werethen placed in the reactor of a commercial fixed bed hydroforming plant.The operation conditions of the commercial plant were varied from timeto time. However, the range of operating conditions was approximately asfollows: pressure 250 p.s.i.g., average temperature 900 to 975 F.,recycle gas (60% H rate 2000 to 3000 cubic feet per barrel of feed,process cycle length 8 hours, approximately 2 cycles per day. Betweencycles the catalyst was regenerated by burning 0E coke deposits withair.

After aging for several months the catalysts were removed from thecommercial plant and tested for hydroforming activity in a fixed bedhydroforming pilot plant operated under the conditions described inExample 26. The following data were obtained:

Table III Feed Rate for 95 Oct. No., W./Hr./W.

Time Aged, Months Catalysts E and 4 contain silica as a stabilizingagent and, therefore, should be compared with each other. Catalyst 4contains 4% silica while catalyst E contains only 2% silica.

The supen'or stability of catalysts D and E is evident when comparedwith catalysts 3, 4, and 5 of similar composition. Here again there wasno significant difference in the yields of products obtained from thesecatalysts.

APPENDIX A.-CATALYST IDENTIFICATION A. A 3% alumina hydrosol wasprepared by hydrolyaing aluminum amylate in the presence of acetic acidpeptizing agent as described in U.S. 2,656,321. Ammonium molybdatesolution was added to give a composition comprising 10% M00 and 90% A1 0The mixture was dried at about 250 F. and calcined at about 1000 F.;

B. A 3% alumina hydrosol was prepared by hydrolyzing aluminum amylate inthe presence of acetic acid peptizing agent as described in U.S.2,656,321. The sol was introduced dropwise into boiling butanol so thatthe water was distilled overhead as an azeotrope with butanol. Afterremoval of the water was complete the alumina was recovered by filteringfrom the butanol and heating in a steam heated oven. The dried aluminawas calcined at l000 F. and impregnated with 10% M00, by soaking in asolution of ammonium molybdate;

C. A solution of aluminum amylate in excess amyl '17 alcohol andpetroleum hydrocarbon solvent was hydrolyzed by mixing with twice itsvolume of water at room temperature. The alumina was dried at 250 F.,calcined for 16 hours at 650 F., and impregnated with 10% M by soakingin ammonium molybdate solution;

D. A 3% alumina hydrosol prepared by hydrolyzing aluminum amylate in thepresence of acetic acid peptizing agent as described in US. 2,656,321was spray dried by spraying into hot flue gas. The alumina was calcinedfor 16 hours at 650 F. and was impregnated with 10% M00 by soaking inammonium molybdate solution;

B. Aluminum amylate solution was hydrolyzed with twice its volume ofwater containing sufficient 3% silica hydrosol to add 2% by weight ofsilica to the alumina product. The 3% silica hydrosol was prepared bytreating dilute sodium silicate solution with an acid regenerated cationexchange resin. The alumina comprising 2% silica was dried at about 250F., calcined at about 1000 F., and impregnated with 10% M00 by soakingin a solution of ammonium molybdate;

(1) The alumina base is the F-10 grade of Alcoa activated aluminaproduced by the Aluminum Co. of America. This alumina is thought to be aproduct of the Baeyer process for alumina purification. The catalyst wasprepared by impregnating the base with 10% M00 by soaking in ammoniummolybdate solution. This catalyst was formerly used in a commercialhydroforming plant;

(2) This commercial catalyst comprises 12% M00 and 88% A1 0 and wasmanufactured by the Oronite Chemical Co. The exact method of manufactureis not known, but it is thought to include the co-precipitation ofalumina (from A101 and molybdena. This catalyst has been employed incommercial hydroforming operations;

(3) This is the prototype batch of the commercial hydroforming catalystmanufactured by the National Aluminate Co. It comprises 10% M00 andabout 2% silica. This catalyst is presently in use in several commercialfluid hydroforming plants. The catalyst was manufactured by mixing asolution of sodium aluminate containing sodium silicate with a solutionof aluminum sulfate containing sulfuric acid. The precipitate wasfiltered, spray dried, washed and impregnated with molybdena by soakingin ammonium molybdate solution;

(4) The alumina base is the XH-42 grade of Alcoa activated aluminacontaining 4% silica manufactured by the Aluminum Co. of America. Thecatalyst was prepared by impregnating the base with 10% M00 (5) This isthe commercial catalyst, comprising of M00 manufactured by the AmericanCyanamid Co. The method of manufacture is not known. This catalyst isemployed in several commercial hydroforming plants.

EXAMPLE 28 The following data in Table IV comparing fresh platinumcatalyst (i.e. not regenerated during the run) were obtained with avirgin naphtha feed stock (200/ 300 F. V.T.) from a West Texas crudehaving the following inspections Distillation:

I.B.P 223 F. 10% 238 F. 50% 257 F. 70% 270 F. F.B.P 317 F. Aniline point124 F. Sulfur 0.6 wt. percent. Gravity 55.4 API. Octane 51.7 Researchclear.

Table IV Catalyst H 7 8 9 Yields:

05+, vol. percent 86.1 82.8 82.1 85.9 04, vol. percent..- 3.6 6. 6 6.53. 2 Dry Gas, wt. percen 6. 5 7. 4 8. 0 7. 2 Distillation 212 F.,percent off on 05-!- product 9 13-16 18 10 Catalyst H.-1 vol. ofaluminum amylate was hydrolyzed with 2 vol. of water at roomtemperature. The organic phase was decanted and the precipitate was thenstripped and dried overnight at 250 F. The alumina was then activated bycalcination at 1100 F. for 4 hours. An amount of chloroplatinic acid(40% Pt) in water just sufficient to wet the calcined alumina Was added.The mixture was then mixed, dried overnight at 250 F. and pilled. Thecatalyst contained 0.6 wt. percent Pt.

Catalyst 7.The alumina base is the H-4l grade of Alorco activatedalumina manufactured by the Aluminum Company of America, and containsabout 5.5% SiO It has a surface area of about 260-320 mF/gm. Thisalumina is impregnated with chloroplatinic acid dried by slow heating ina hydrogen atmosphere to 900 F. It contains 0.5% Pt;

Catalyst 8.-Obtained from the American Cyanamid Co. Believed to be agamma form of alumina. It is a pilled catalyst /s x A3") containing 0.6Wt. percent Pt and having a surface area of 209 m. /gm. and apermeability 1 of 1.4;

Catalyst 9.-Obtained from Baker and Co., Inc. Identified as RD150. It isan extruded catalyst 0A x /s) containing 0.6 wt. percent Pt andinitially 1.7% Cl. It has a surface area of 358 m. gm. and apermeabiiity 1 of 15.

These data show that the catalyst of this invention is more selective toC gasoline than the prior art catalysts.

EXAMPLE 29 The following data comparing an alcoholate alumina platinumcatalyst with its nearest competitor in performance in Table IV,catalyst #9, were obtained using a feed stock (250/325 F. V.T.) havingthe following inspections:

Distillation:

I.B.P 255 F.

F.B.P 327 F. Aniline point 126 F. Sulfur 0.001 wt. percent. Gravity 57.7API. Octane 53 clear Research.

The alcoholate alumina catalyst, catalyst I used in this test wasprepared by hydrolyzing an aluminum alcoholate diluted with ahydrocarbon solvent with water containing about 2.4 wt. percent NH agingthe precipitate for 9 hours, stripping with steam to remove solvent andalcohol, filtering the precipitate, drying at 250 F.,

1 (Ce/min. of dry Na diffusing through pill 5 x 5 mm. at one atm.press.)

19 grinding the alcoholate alumina, activating at 1050 F. for 4 hours,impregnating with chloroplatinic acid sufficient to obtain 0.6 wt.percent Pt on the catalyst, drying at 250 F., pilling, and calcining 1hour at 1100 F.

The catalyst-was contained in 4 reactors in series, each consisting ofinsulated one inch extra heavy stainless steel pipe. The conditionswere: over-all space velocity- 1 W./hr./w.; pressure400 p.s.i.g.;hydrogen rate5000- 6000 s.c.f./bbl. The C product selectivity wasmaintained between 84.5 and 86.2 throughout the run. The temperature,both preheat and reheat between the reactors, was adjusted throughoutthe run to maintain a 94-96 clear Research octane number product. A logof time versus temperature required for a 95 octane product is shown inTable V.

Table V Temperature, F., for 95 O. N.

The data in Table V illustrate the high activity of the alcoholatealumina base catalyst because the feed preheat requirementis-substantially lower. The average feed preheat requirement for thealcoholate alumina base catalyst is about 12-15 F. lower, indicatingthat the absolute activity of this catalyst is higher. These data alsoillustrate the high stability of the alcoholate alumina base catalyst. A300-hour run with an 84.5% CH- yield after five regenerations hasindicated that a six months catalyst life is possible.

The platinum-containing catalysts prepared in accordance with thepresent invention are particularly suitable for hydroforming hydrocarbonfractions boiling within the motor fuel or naphtha range. In suchhydroforming operations, temperatures are usually between 600l050 F.,preferably 800950 F., the pressure between atmospheric and 1000 poundsper square inch, and hydrogen or hydrogen-rich recycle gas isrecirculated through the reaction zone at a rate of about 1000-12,000,preferably about 6000, cubic feet per barrel of feed. This hydrogenrich:gas contains at least about 60 volume percent hydrogen, preferably80-99% hydrogen by volume. The oil feed rate in a fixed bed operation isabout 0.25 to about 4.0 v./v./hr. (volume of liquid feed naphtha pervolume of catalyst per hour), preferably l-2 v./v./hr.

It will be understood that these catalysts are equally suitable for usein 'a fluidbed type operation. Accordingly, these catalysts may be usedeither in the form of pills or in the form of a finely divided powder.They may also be converted into microspheres, according to the generaltechniques described in my prior patent, US. 2,636,865. This may beaccomplished either by emulsifying an alumina hydrosol with naphtha, asdescribed therein, using aerosol as an emulsifying agent. Such ahydrosol may be prepared directly in the hydrolysis, or by peptizing theinitial gel slurry, and the hydrosol may be dried directly in the formof microspheres by the spray dryingtechnique. The impregnation withplatinum may take :place at any stage of this process, either before orafter the .hydrosol is formed and dried or spray dried.

The catalysts prepared as described above give good resultsinh'ydr'oforming operations at high pressures of from about 500-1000p.s.i.g., but they are especially effective at low pressures ofthe'order of from 50-400 p.s.i.g. These catalysts are also useful in a widevariety of hydrocarbon conversion reactions or'similar reactions wherehydrogen transfer to or from a hydrocarbon chain is involved, includinghydrogenation, dehydrogenation, cyclization, isomerization, alkylationor polymerization reactions and the like.

Although in the examples given above the catalytic materials made bythis process were dried at a temperature of 250 F. and activated byheating at about 850- 900 F., these temperatures may be varied. Thus,the activation may be accomplishedby heating to a temperature within arange of 850l450 F., for a suitable period, such as from one to eighthours, or the activation may be limited entirely to that obtained byplacing the dried catalyst in the reaction zone and bringing it up toreaction temperature for use in hydroforming or the like.

In hydrocarbon conversion operations such as hydroforming at arelatively low total pressure, where carbonaceous material is depositedon the catalyst, it is contemplated that the catalyst will beregenerated by treating with a regenerating gas such as diluted air orhydrogen or other suitable gas, and the regenerated catalyst reused. Itis also contemplated that the catalyst be treated with a halogencompound, preferably chlorine or hydrogen chloride before, during orafter the regeneration treatment.

The foregoing examples are merely'illustrative of the present invention.It will be understood that numerous variations are possible withoutdeparting from the scope of the following claims.

What is claimed is:

l. A process for manufacturing naphtha reforming catalysts whichcomprises preparing a solution of an aluminum alcoholate, hydrolyzingsaid solution to form high purity alcoholate alumina, compositing thisalcoholate alumina with an active reforming catalyst, drying andcalcining the resultant product to activate the same.

2. A process for manufacturing naphtha reforming catalysts whichcomprises preparing a solution of an aluminum alcoholate, hydrolyzingsaid solution to form high purity alcoholate alumina, compositing thisalcoholate alumina with a group VI metal oxide, drying and calcining theresultant product to activate the same.

3. A process for manufacturing naphtha reforming catalysts whichcomprises preparing a solution of an aluminum alcoholate, hydrolyzingsaid alcoholate with an aqueous medium to form a hydrous aluminatherefrom, drying said hydrous alumina to form high purity alcoholatealumina base, impregnating said base with a solution of a platinum groupmetal compound, drying said impregnated alcoholate alumina base andcalcining the resultant product to activate the same.

4. A process for manufacturing a platinum-alumina catalyst whichcomprises preparing a solution of an aluminum alcoholate, hydrolyzingsaid solution to form high purity alcoholate alumina and compositingthis alcoholate alumina withan aqueous solution containingchloroplatinic acid, drying and calcining the resultant product toactivate the same.

5. A process for manufacturing a platinum-alumina catalyst whichcomprises preparing a solution of an aluminum alcoholate, hydrolyzingsaid solution to form high purity alcoholate alumina and compositingthis alcoholate alumina with an aqueous solution containingchloroplatinic acid and an added halogen compound, drying and calciningthe resultant product to activate the same.

6. A catalyst composition for the reforming of naphtha boiling rangehydrocarbons comprising an active reforming catalyst agent-supported onhigh purity alcoholate alumina base 7. A catalyst composition for thereforming of naphtha boiling range hydrocarbons comprising .a group VImetal oxide supported on a high purity alcoholate alumina base.

8. A catalyst composition for the reforming of naptha boiling rangehydrocarbons comprising a platinum group metal supported on a highpurity alcoholate alumina base.

9. A catalyst composition for the reforming of naphtha boiling rangehydrocarbons comprising 0.01 to 2.0 wt. percent platinum supported on ahigh purity alcoholate alumina base.

10. The method of hydroforming hydrocarbon fractions boiling within thenaphtha or motor gasoline boiling range which comprises passing thevaporized hydrocarbon feed stock in admixture with hydrogen-rich gasthrough a hydroforrning reaction zone, maintaining the naphtha vaporsand hydrogen-containing gas in contact with a catalyst comprising anactive reforming catalyst agent supported on a high purity alcoholatealumina base at active hydroforming conditions of temperature andpressure for a period suflicient to substantially increase the octanenumber of said hydrocarbon fraction.

11. The method of hydroforming hydrocarbon fractions boiling within thenaphtha or motor gasoline boiling range which comprises passing thevaporized hydrocarbon feed stock in admixutre with hydrogen-rich gasthrough a hydroforming reaction Zone, maintaining the naphtha vapors andhydrogen-containing gas in contact with a catalyst comprising a group VImetal oxide supported on a high purity alcoholate alumina base at activehydroforming conditions of temperature and pressure for a periodsufiicient to substantially increase the octane number of saidhydrocarbon fraction.

12. The method of hydroforming hydrocarbon fractions boiling within thenaphtha or motor gasoline boiling range which comprises passing thevaporized hydrocarbon feed stock in admixture with hydrogen-rich gasthrough a hydroforming reaction zone, maintaining the naphtha vapors andhydrogen-containing gas in contact with a platinum group metal supportedon a high purity alcoholate alumina base at active hydroformingconditions of temperature and pressure for a period sufficient tosubstantially increase the octane number of said hydrocarbon fraction.

13. The method of hydroforming hydrocarbon fractions boiling with thenaphtha or motor gasoline boiling range which comprises passing thevaporized hydrocarbon feed stock in admixture with hydrogen-rich gasthrough a hydroforming reaction zone, maintaining the naphtha vapors andhydrogen-containing gas in contact with a catalyst comprising 0.01 to2.0 wt. percent platinum supported on a high purity alcoholate aluminabase at active hydroforming conditions of temperature and pressure for aperiod suificient to substantially increase the octane number of saidhydrocarbon fraction.

14. The process for hydroforming hydrocarbon feed stock boiling in thenaphtha boiling range which comprises vaporizing the feed stock, passingthe vapors together with preheated hydrogen-containing gas through ahydroforming reaction zone maintained at a reforming temperature betweenabout 750 F. and 1050" F. and pressure between atmospheric and 1000p.s.i.g., maintaining the naphtha vapors in contact with a catalystcomprising 0.01 to 2.0 wt. percent platinum supported on a high purityalcoholate alumina for a period sufficient to substantially increase theoctane number of said hydrocarbon feed stock.

15. The process for hydroforming hydrocarbon feed stock boiling in thenaphtha boiling range which comprises vaporizing the feed stock, passingthe vapors together with preheated hydrogen-containing gas through ahydroforming reaction zone maintained at a reforming temperature betweenabout 850 and 975 F. and pressure between and 400 p.s.i.g., maintainingthe naphtha vapors in contact with a catalyst comprising 0.01 to 2.0 wt.percent platinum supported on a high purity alcoholate alumina for aperiod sufiicient to substantially increase the octane number of saidhydrocarbon feed stock.

References Cited in the file of this patent UNITED STATES PATENTS2,636,865 Kimberlin Apr. 28, 1953 2,746,937 Hunter et al. May 22, 19562,773,810 Kimberlin et al. Dec. 11, 1956 2,776,264 Dinwiddie et al. Jan.1, 1957

11. THE METHOD OF HYDROFORMING HYDROCARBON FRACTIONS BOILING WITHIN THENAPHTHA OR MOTOR GASOLINE BOILING RANGE WHICH COMPRISES PASSING THEVAPORIZED HYDROCARBON FEED STOCK IN ADMIXTURE WITH HYDROGEN-RICH GASTHROUGH A HYDROFORMING REACTION ZONE, MAINTAINING THE NAPHTHA VAPORS ANDHYDROGEN-CONTAINING GAS IN CONTACT WITH A CATALYST COMPRISING A GROUP VIMETAL OXIDE SUPPORTED ON A HIGH PURITY ALCOHOLATE ALUMINA BASE AT ACTIVEHYDROFORMING CONDITIONS OF TEMPERATURE AND PRESSURE FOR A PERIODSUFFICIENT TO SUBSTANTIALLY INCREASE THE OCTANE NUMBER OF SAIDHYDROCARBON FRACTION.